Chemical product and process for preparing same



Patented Aug. 6, 1935 UITED STTE CHEMICAL PRODUCT AND PROCESS PREPARING SAME FOR Arnold M. Collins,Wilmington, DeL. assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application January 9, 1934, Serial No. 705,893

' 22 Claims.

chloric acid with various protein materials. Still Gil more particularly it relates to the preparation of films, plastics, coating compositions, adhesives, etc., from aqueous dispersions of the polymerized addition product intermixed with aqueous dispersions of protein materials.

This application is a continuation in part of application, Serial No. 537,484, filed May 14, 1931.

This invention has as an object the preparation of new and useful compositions of matter. A further object is to prepare dispersions of chloro- 2-butadiene-l,3 polymer containing substantial amounts of various protein materials. A still further object is to prepare useful articles from such dispersions.

It has been found that either acid or alkaline aqueous dispersions of polymerized chloro-2- butadiene-1,3 may be modified in properties by incorporating such protein materials as gelatin, glue, casein, etc., in the form of aqueous solutions ordispersicns. The ratio of polymerized chloro- 2-butadiene-1,3 to protein may be varied from one part polymerized chloro-2-butadiene-1,3 with nine parts protein to nine parts polymerized chloro-2-butadiene-L3 with one part protein.

Aqueous alkaline dispersions of polymerized chloro-2-butadiene-l,3 which are described in the application, of which this application is a continuation in part, and aqueous acid dispersions of polymerized chloro-2-butadiene-1,3 which are described in an applicationof J. E. Kirby, Serial No. 572,739, filed Nov. 2, 1931, may be prepared as follows:

Alkaline dispersion of polymerized chloro-z- Fresh chloro-2-butadiene-1,3 is added slowly and with vigorous mechanical agitation to an equal weight of a 2% aqueous solution of sodium oleate. When the emulsification has been completed, the emulsion is stored at 10 C. for twenty-four to forty-eight hours. During this period of storage the chloro-2-butadiene-1,3 undergces polymerization and a dispersion of polymerized insoluble polymer results. Enough ammonia is added to render the dispersion slightly alkaline, after which it is ready for use. Antioxidants which have been previously dispersed in 2% aqueous sodium oleate solution may be incorporated at this point if desired. This incorporation is efiected by mixing the antioxidant dispersion with the dispersion of polymerized chloro-Z-butadiene-IB. Phenyl-beta-naphthylamine is a suitable antioxidant for this purpose and may be incorporated to the extent of 1%,

based on the weight of polymer in the emulsion. 5

polymerized chloro-Z-buta- (liens-1,3

Acid dispersion of both dispersions be either alkaline or acid. Thus, 20

an acid casein dispersion may be combined with an acid chloro-2-butadiene-L3 polymer dispersion but an acid casein dispersion cannot be combined with an alkaline chloro-2-butadiene-1,3

polymer dispersion without causing coagulation 26 ofthe polymer. When aqueous dispersions of polymerized chloro-2-butadiene-1,3, especially of the alkaline type, are mixed with aqueous dispersions of protein material, they give products which are useful for a variety of purposes, such as adhesives for safety glass inner layers, molding compositions, vehicles for'c'old water paints, sizing compositions for paper, etc. The prepara tion of these materials is illustrated in the following examples:

Example 1 16.6 parts of casein are added to 83.4 parts of water and the mixture is allowed to stand for two or three hours in order to effect a thorough soaking of the casein. The mixture is then warmed to 60-80" C. and ammonia water (specific gravity 0.90) is added in portions until a persistent ammoniacal odor is obtained. Swelling of the casein begins as soon as the ammonia is added. This swelling is hastened by. stirring. In case unswollen lumps persist after stirring, more ammonia is added. Finally, a smooth milb dispersion is obtained which is allowed to age for twenty-four hours before use.

100 parts of the above casein dispersion is added with constant stirring to 106 parts of a 47% aqueous alkaline dispersion of polymerized chloro-2 -butadiene-1,3 containing 5 cc. of ammonia water (specific gravity 0.90). The mixture sometimes tends to solidify after the first addition of casein but as more casein is added, a. drop in viscosity occurs and a smooth dispersion is finally obtained. 'This dispersion is allowed to age for twenty-four hours before use in order to eliminate any undispersed particles that may be present. The final dispersion contains chloro-2-butadiene-l,3 polymer and casein in the ratio of 3:1 and has a total solids content Example 2 25 parts of casein is kneaded with 75 parts of lacial acetic acid until the casein is well dispersed. The resulting jellyis then diluted with water until a solids content of 14.5% is reached.

50 parts of the above casein dispersion is added with constant stirring to 22.7 parts of a. 4

7 acid aqueous dispersion of chloro-2-butadiene-1,3

polymer, prepared as previously described. The

resulting dispersion is allowed to stand for twenty four hours before use. This dispersion contains casein and chloro-2-butadiene-1,3 polymer in the ratio of 1.6:1.

Example 3 lowed to age for twenty-four hours to remove 7 any incompletely dispersed particles.

This composition contains gelatin and chl0ro-2-butadiene- 1,3 polymer in the ratio of 1:3 and has a solids content of 12.7%.

Glue may be substituted for gelatin in Example 3, or may be incorporated as described in the following example.

Example 4 A solution of glue in water is made slightly' alkaline with ammonium hydroxide and enough of this solution is added to a standard polymerized latex to provide one part of glue for each four parts of chloro-2-butadiene-1,3. To the resulting homogeneous emulsion a small amount of a colloidal solution of phenyl-beta-naphthyl amine is added. The latex thus produced yields a stiff film very resistant to tear,

The following example illustrates the preparation of a safety glass sandwich using a gelatinchloro-2-butadiene-1,3 polymer composition.

Example 5 Two glam plates of any suitable size or thickness are thoroughly cleansed on one side with soap solution or other suitable composition which will remove dirt or grease. The clean surfaces are then coated by any suitable means, for example, by spraying with an aqueous alkaline dispersion of gelatin and chloro-2-butadiene-l,3 polymer having the following composition:

, Parts Gelatin 1 Chloro-2-butadiene-1,3 polymer 2 Water 57 This composition is prepared by blending an aqueous solution of gelatin with an aqueous alkaline dispersion of chloro-2-butadiene-1,3 polymer as previously described. After this composition has been applied to the glass it is allowed to dry. A sheet of pyroxylin (nitro-cellulose) or other suitable inner layer material is next placed between the two coated glass surfaces and the resulting sandwich is compressed and heated in the usual manner. A suitable pressure is L50 pounds per square inch at a temperature of 110 0., said pressure and temperature being maintained for five minutes. A sandwich prepared in this manner shows no bubbles on release of pressure, is perfectly transparent, and shows good resistance to impact tests. Moreover, the index of refraction of the, gelatin-chloro-2-butadiene- 1,3 polymer film is the same as that of pyroxylin with .the result that any surface irregularities in the pyroxylin, such as sheeter lines, are masked by the adhesive film after the heat and pressure treatment. This feature permits the use of an unpolished pyroxylin sheet as the inner layer, with consequent elimination of any expensive polishing operation.

Numerous modifications of this process are possible. For example, the pyroxylin inner layer may be omitted and the protein-chloro-2-buta diene-1,3 polymer film may be used as a combined adhesive and inner layer. Furthermore the pyroxylin may be replaced by various esters Example 6 v I 20 parts of glue is added to parts of water at a temperature of 60-80 C. and the mixture is stirred until the glue has completely dissolved. parts of a 47% aqueous alkaline dispersion of polymerized chloro-2-butadiene-L3, containing 5 cc. of ammonia water (specific gravity 0.90) is added to parts of the 20% glue solution,.

described above, and the mixture is stirred until completely blended. (2.5% based on the glue content of the size) may be added if desired to effect a hardening of the glue after application to the paper.

The paper to be sized is passed througha bath of glue-polymer dispersion after dilution with Example 7 Thev following ingredients are ground in a ball mill for forty-eight hours to obtain a pigmented base;

Mill base Parts 16.6% casein dispersion (prepared as in Example 1) 300 Concentrated ammonia water (specific gravity 0.90)-. Zinc oxide 100 Thismill base is then blended with an aqueous Alum or formaldehyde aoiopia dispersion of chloro-2-butadiene-1,3 polymer in the following proportions:

Parts Mill base 50 Alkaline chloro 2 butadiene 1,3 polymer dispersion (47% solids) 22 2% sodium silicate solution Formaldehyde (2.5% based on casein) may be added if desired to efiect an insolubilizing and hardening of the casein after applicatlon of the paint. The purpose of the sodium silicate is to precipitate soluble salts which may be present in the zinc oxide and which would tend to cause coagulation of the polymer dispersion unless removed. This cold water paint can be applied by spraying, brushing, etc., and dries to a tough, flexible film which is useful as a finish on beaver board, pressed board, leather, metal, glass, etc., and as a sealer or size coat on plaster. Other pigments may be incorporated to produce a variety of colors, and the ratio of ingredients may be varied to obtain variations in hardness, flexibility, etc. Other modifying agents in the form of aqueous dispersions in water may also be incorporated as, for example, dispersions of waxes, asphalts, synthetic and natural resins, drying oils, etc. Paints or this type are particularly useful where oil and grease resistance is desired. Theplasticizing properties of chloro-2-butadiene-1,3 polymer for protein materials may also be utilized in the preparation of plastics and molding materials, as for example, in the preparation of casein plastics. The preparation of a casein plastic containing chloro-2-butadiene-1,3 polymer is illustrated by the following example:

Example 8 108 parts of dry rennet casein is introduced.

into a steam heated kneading machine such as a Werner-Piieiderer mixer. 380 parts of water containing 16.5 cc. of concentrated ammonia water (specific gravity 0.90) is added and the pohnds per square inch and a temperature -of 90 C., both maintained for a period of fifteen minutes are suitable for molding. The extruded or molded plastic is then placed in a bath of formaldehyde to harden the casein. Pigments may be incorporated during the kneading process, if desired, preferably in the form of a suspension-of the pigment in dilute casein solution.

An alternative procedure for preparing plastics of this type consists in drying and powdering the kneaded plastic after removal from the mixer, followed by,incorporation of a suitable hardening agent with the powdered material and molding in a die, under heat and pressure. Suitable hardening agents are resins which liberate formaldehyde at the molding temperature and thus harden the plastic in the mold. Dimethylol urea, condensation products of dimethylol urea with formaldehyde, or condensation products of diphenylol propane with formaldehyde have been found to be effective in this connection. Plastics prepared in this manner do not require further hardening in formaldehyde solution.

Plastics prepared as described above are less afiected by moisture than casein plastics-contain- 'ing such water soluble plasticizing agents as glycerol, Turkey red oil, etc. They also show less shrinkage after the formaldehyde hardening process and can stand greater shock without shattering than similar casein plastics which contain no chloro-2-butadiene-l,3 polymer.

The plasticizing properties of chloro-Z-buta- .diene-l,3 polymer for protein materials may be further utilized in the preparation of coated fabrics as, for example, in the preparation of gasresistant fabrics (balloon fabric) and in the preparation of oil and grease resistant hose. Glue is often used as a coating composition for this purpose clue to its impermeability to both gases and oils. Fabrics of this type are improved if polymerized chloro-2-butadiene-1,3 is incorporated with the glue since the polymer increases both the water resistance and pliability of the glue without eiiecting any sacrifice in its oilresisting properties.

Theterm aqueous dispersion oi polymerize d chloro-2-butadiene-1,3 (or aqueous dispersion of chloro 2 butadiene 1,3 polymer) used throughout this specification applies to aqueous dispersions however prepared, and to the use of halogenated 1,3-butadienes other than chloro-Z- butadiene-Lii as, for example, bromo-Z-butadime-1,3. In general, it includes any of the aqueous'dispersions disclosed in applicants copending application, Serial No. 537,484, or in Kirby application, Serial No. 572,739, referred to above.

The term protein" is intended to cover such materials as casein, gelatin, glue, blood and egg albumin, collagen, gluten, gliadin, etc., or mixtures of these materials in any proportions. Furthermore, we do not wish to be limited to any particular source or method of preparing the protein material. Dispersions of protein utilizing ammonia as the dispersing or swelling agent have been cited in the previous examples, especially in the case of casein dispersions. Instead of ammonia, however, other alkaline materials such as borax, trisodium phosphate, sodium carbonate, ammonium carbonate, caustic soda, etc., may be used to good advantage for this purpose.

While this invention is concerned primarily with the addition of the protein solution tothe aqueous dispersion of polymerizedchloro-Z-buta- (heme-1,3, it is feasible to operatein the reverse manner especially in the case of acid media. It is possible, for example, to prepare the protein solution or dispersion, add chloro-2-butadiene- 1,3 monomer, and then polymerize. This variation of the invention represents, however, a definitely less preferred embodiment because of the greatly decreased rate of polymerization of the chloro-2-butadiene-L3.

The products prepared according to this invention are useful as adhesives for safety glass inner layers, as plastics and molding compositions, as vehicles for cold water paints, as laminating agents, as impregnating and coating compositions, as finishes for leather, and in other applications in which protein materials gener ally find use.

A film deposited from the composition described in Example 1, namely, the mixture of casein and chloro-2-butadlene-1,3' polymer, is tough, translucent, and flexible, and adheres well to practically all surfaces, A film deposited from v film. This is not true of natural rubber latex, which gives cloudy films with gelatin and'ca'sein.

The transparency of the gelatin-chloro-2-butadime-1,3 polymer film described under'Exam pie 3 makes it useful as a laminating agent for regenerated cellulose and as an adhesive for the pyroxylin inner layer of safety glass. The composition described under Example 1 can be utilized as a vehicle for cold water paints and in the sizing of paper, cardboard, etc., where unusual oil and grease resistance is desi Chloro-2-butadiene-1,3 polymer is an effective plasticizing agent for protein materials. This plasticizing effect is obtained without adversely aflecting the transparency of the protein material in case it is utilized as a film. Furthermore, since chloro-2-butadien-1,3 polymer is very resistant to'water, it improves the water resistance of protein materials with which it is incorporated. This is not true of such commonly used protein softeners .as glycerol, Turkey red oil, etc. In addition, the oil and grease resisting properties of protein materials are not adversely affected by the incorporation of chloro-2-butadiene-1,3

polymer, since the latter material has unusual oil and grease resistance. V

The. incorporation of protein materials in aqueous dispersions of chloro-2-butadiene-1,3

polymer results in amarked stabilization of the dispersions toward mechanical handling and toward precipitation by electrolytes. This enables modified chloro-2-butadiene-1,3 polymer dispersions to be sprayed, brushed, or. spread without precipitation or the formation of lumps. The wetting properties of the modified chloro-2-butadime-1,3 dispersions toward glass, fabric, paper, etc., are also greatly improved by the incorporation of. protein materials. Finally, protein'materials, dueto their amphoteric properties act as acid'acceptors and combine with the small amounts of acid sometimes liberated from the polymer under the influence of heat or light. This tends to stabilize compositions prepared from chloro-'-2- butadiene-1,3 polymer; Other advantages of the invention will be apparent from the above description and specific examples;

It is apparent that many widely diife'rent embodiments of this invention may be made with"- of, and therefore the invention is not to be limited except as indicatedin the appended claims.

' I claim: v

1. An aqueous dispersion brskthaiogen-z butadiene-L3 and protein in which t'he ratio of one to the other is never greater than 9:1.

2. An aqueous dispersion of a halogen- 2'- butadien,e- 1,3 polymer and protein in which the ratio of onegto 9:1.- I g q aqueous 'of chloro-2-butacliche-1,3 and protein inwhich the ratio of one-to theother is never'groaterthan 9:1. v

4. An aqueous dispersion of chloro-2-butadie'ne-'-1,3 polymer and protein inwhich-the ratio 'of-oneto'theother is never greater 9:1.

the other is never greater than never greater than 9 5. An aqueous dispersion of chloro-2-butadiene-1,3 polymer and protein in which the ratio of one to the other. is never greater than 9:1, to

which has been added an emulsifying agent.

6. An aqueous dispersion of 'chloro-2-butadiene-1,3 polymer and protein in which the ratio of one to the other is never greater than'ilzl, to which has been added a soap.

7. An aqueous alkaline dispersion of chloro-.

2-butadiene-L3 polymer and protein in which the ratio of one to the other is never greater than 9:1.

8. An aqueous alkaline dispersion of chloro- 2-butadiene 1,3'.polymer and protein in which the ratio of one to the other is never greater than 9: 1, to which has been added a fatty acid soap.-

9. An aqueous dispersion comprising a chloro- 2-butadiene- 1,3 polymer and protein in which the ratio of one to the other is never greater than 9:1, obtained by polymerizing an emulsion of chloro-2-butadiene-1,3 and then adding the dispersio'n to a dispersion of the protein.

10. A plastic product containing a chloro-2- butadiene-1,3.polymer and protein in-which the ratio of one to the other is neyer greater than 9: 1.

11. An aqueous dispersion of a bromo-z-butadiene-1,3 polymer and protein in which the ratio of one to the other is never greater than 9: 1.

12. An'aqueous dispersion of achloro-2-butadiene-l,3 polymer and glue in which the ratio of one to the other is never greater than 9:1.

13. An aqueous dispersion of a chloro-2-butadime-1,3 polymer and gelatin in which the ratio of one to the other is never greater than 9:1.

14. An aqueous dispersion of a chloro-2-butadime-1,3 polymer and casein in which the ratio of one to the oth'eris never greater than 9:1.

15. An aqueous alkaline dispersion of,a chloro- 2-butadiene-1,3 polymer and casein in which the ratio of one to the other is never greater than 9:1.

16.'An aqueous acid dispersion of a chloro-2- butadiene-1,3 polymer and casein in which the ratio of one to the other is never greater than 9:1, obtained by polymerizing chloro- 2-butadiene-1,3 dispersed in an acid solution containing a small amount of casein, separately dispersing casein in an acid solution and then adding the casein disto the polymerized chloro-2-butadienepers'ion 1,3.

17..A method of preparing aqueous alkaline dispersions of protein and chloro-2-butadiene-1,3 polymer which comprises emulsifying the chloro- 2-butadiene-1,3 in water, polymerizing the emulsified chloro-2-butadiene-1,3 and adding an alkali, separately emulsifying the protein in an aqueous alkaline solution then adding the protein to the ch1oro-2-butadiene-1,3 and ageing the resulting dispersion. out departing fromthe spirit and scope there- 18. A method of preparing aqueous alkaline dispersions of casein and chloro-2-butadiene-l,3 polymer which comprises emulsifying the chloro- 2-butadiene-L3 in water, polymerizing the emulsifiedchloro-2-butadiene-L3 and adding an alkali, separately emulsifying the casein in an aqueous alkaline solution then adding the casein to the chloro-2-butadiene-1,3 and ageing the resuiting dispersion.

19}. The process of preparing an aqueous dispersionof chloro-2-butadiener-L3 polymer and casein in. which the ratio of one to theKother-is v :1'w comprises dispersing the vchloro-2--butadiene-1,3.in an aqueous acid 'solution to'which has been added a small amoimt {of oasein, .polymerizing the dispersed chloro- 2- .butadiene-1,3,separately the casein in 2,010,012 an aqueous acid solution, then adding the casein dispersion to the chloro-2-butadiene-L3 dispersion and ageing the resulting dispersion.

20. An aqueous acid dispersion of chloro-Z- butadiene-1,3 polymer and protein in which the 10 dime-1,3 in water, polymerizing the emulsified merized chloro-2-butadiene-1,8 to an aqueous dispersion of the protein.

22. A process of preparing aqueous dispersions of protein and chloro-Z-butadiene-Lii which comprises adding an aqueous dispersion of protein to an aqueous dispersion of chloro-2- butadime-1,3 and then polymerizing the dispersed chloro-2-butadiene-L3.

ARNOLD M. COLLINS.

chloro-2-butadiene-.1,3 and then adding the poly- 

